JP2004075987A - Polytetrafluoroethylene-containing powder and thermoplastic resin composition using the same - Google Patents
Polytetrafluoroethylene-containing powder and thermoplastic resin composition using the same Download PDFInfo
- Publication number
- JP2004075987A JP2004075987A JP2003170673A JP2003170673A JP2004075987A JP 2004075987 A JP2004075987 A JP 2004075987A JP 2003170673 A JP2003170673 A JP 2003170673A JP 2003170673 A JP2003170673 A JP 2003170673A JP 2004075987 A JP2004075987 A JP 2004075987A
- Authority
- JP
- Japan
- Prior art keywords
- polytetrafluoroethylene
- thermoplastic resin
- containing powder
- dispersion
- powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- -1 Polytetrafluoroethylene Polymers 0.000 title claims abstract description 95
- 229920001343 polytetrafluoroethylene Polymers 0.000 title claims abstract description 79
- 239000004810 polytetrafluoroethylene Substances 0.000 title claims abstract description 79
- 239000000843 powder Substances 0.000 title claims abstract description 49
- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 27
- 239000011342 resin composition Substances 0.000 title claims abstract description 12
- 229920000642 polymer Polymers 0.000 claims abstract description 16
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical group CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000006185 dispersion Substances 0.000 claims description 33
- 239000002245 particle Substances 0.000 claims description 26
- 239000003995 emulsifying agent Substances 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 9
- 238000001694 spray drying Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000005345 coagulation Methods 0.000 claims description 4
- 230000015271 coagulation Effects 0.000 claims description 4
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 claims description 3
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 230000001112 coagulating effect Effects 0.000 claims 1
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 7
- 238000000465 moulding Methods 0.000 abstract description 6
- 238000010586 diagram Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000008188 pellet Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 8
- 229920000098 polyolefin Polymers 0.000 description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 8
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 7
- 239000000945 filler Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 229920000578 graft copolymer Polymers 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N Bisphenol A Natural products C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 238000003490 calendering Methods 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 229920000620 organic polymer Polymers 0.000 description 4
- 229920006122 polyamide resin Polymers 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 229920000515 polycarbonate Polymers 0.000 description 4
- 229920001955 polyphenylene ether Polymers 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 239000002023 wood Substances 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 238000000071 blow moulding Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 239000000123 paper Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229920005672 polyolefin resin Polymers 0.000 description 3
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-SZSCBOSDSA-N 2-[(1s)-1,2-dihydroxyethyl]-3,4-dihydroxy-2h-furan-5-one Chemical compound OC[C@H](O)C1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-SZSCBOSDSA-N 0.000 description 2
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Natural products OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 2
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 2
- 229920006358 Fluon Polymers 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 239000002211 L-ascorbic acid Substances 0.000 description 2
- 235000000069 L-ascorbic acid Nutrition 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- FOTQZDGLPLCBED-UHFFFAOYSA-N OOOO.CC(C)C1=CC=CC=C1C(C)C Chemical compound OOOO.CC(C)C1=CC=CC=C1C(C)C FOTQZDGLPLCBED-UHFFFAOYSA-N 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 2
- 239000001639 calcium acetate Substances 0.000 description 2
- 235000011092 calcium acetate Nutrition 0.000 description 2
- 229960005147 calcium acetate Drugs 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 210000000497 foam cell Anatomy 0.000 description 2
- 238000010097 foam moulding Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 229920005669 high impact polystyrene Polymers 0.000 description 2
- 239000004797 high-impact polystyrene Substances 0.000 description 2
- 239000010903 husk Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- 238000003856 thermoforming Methods 0.000 description 2
- UIYCHXAGWOYNNA-UHFFFAOYSA-N vinyl sulfide Chemical compound C=CSC=C UIYCHXAGWOYNNA-UHFFFAOYSA-N 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- APAUNQLFVGBQQW-UHFFFAOYSA-N (1,2,2-trimethylcyclohexyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1(C)CCCCC1(C)C APAUNQLFVGBQQW-UHFFFAOYSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- ORYGKUIDIMIRNN-UHFFFAOYSA-N 1,2,3,4-tetrabromo-5-(2,3,4,5-tetrabromophenoxy)benzene Chemical compound BrC1=C(Br)C(Br)=CC(OC=2C(=C(Br)C(Br)=C(Br)C=2)Br)=C1Br ORYGKUIDIMIRNN-UHFFFAOYSA-N 0.000 description 1
- WVAFEFUPWRPQSY-UHFFFAOYSA-N 1,2,3-tris(ethenyl)benzene Chemical compound C=CC1=CC=CC(C=C)=C1C=C WVAFEFUPWRPQSY-UHFFFAOYSA-N 0.000 description 1
- DEIGXXQKDWULML-UHFFFAOYSA-N 1,2,5,6,9,10-hexabromocyclododecane Chemical compound BrC1CCC(Br)C(Br)CCC(Br)C(Br)CCC1Br DEIGXXQKDWULML-UHFFFAOYSA-N 0.000 description 1
- VDYWHVQKENANGY-UHFFFAOYSA-N 1,3-Butyleneglycol dimethacrylate Chemical compound CC(=C)C(=O)OC(C)CCOC(=O)C(C)=C VDYWHVQKENANGY-UHFFFAOYSA-N 0.000 description 1
- BSWWXRFVMJHFBN-UHFFFAOYSA-N 2,4,6-tribromophenol Chemical compound OC1=C(Br)C=C(Br)C=C1Br BSWWXRFVMJHFBN-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JJBFVQSGPLGDNX-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)COC(=O)C(C)=C JJBFVQSGPLGDNX-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- BEWCNXNIQCLWHP-UHFFFAOYSA-N 2-(tert-butylamino)ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCNC(C)(C)C BEWCNXNIQCLWHP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000609240 Ambelania acida Species 0.000 description 1
- 239000004156 Azodicarbonamide Substances 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 241000195649 Chlorella <Chlorellales> Species 0.000 description 1
- 241000207199 Citrus Species 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000238557 Decapoda Species 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 244000017020 Ipomoea batatas Species 0.000 description 1
- 235000002678 Ipomoea batatas Nutrition 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000004420 Iupilon Substances 0.000 description 1
- 240000007049 Juglans regia Species 0.000 description 1
- 235000009496 Juglans regia Nutrition 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- GXCLVBGFBYZDAG-UHFFFAOYSA-N N-[2-(1H-indol-3-yl)ethyl]-N-methylprop-2-en-1-amine Chemical compound CN(CCC1=CNC2=C1C=CC=C2)CC=C GXCLVBGFBYZDAG-UHFFFAOYSA-N 0.000 description 1
- 229920003355 Novatec® Polymers 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 241000237502 Ostreidae Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229920006361 Polyflon Polymers 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 1
- SFFTXLYPBWITRH-UHFFFAOYSA-N [2,3-di(propan-2-yl)phenyl] dihydrogen phosphate Chemical compound CC(C)C1=CC=CC(OP(O)(O)=O)=C1C(C)C SFFTXLYPBWITRH-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000012874 anionic emulsifier Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 1
- 235000019399 azodicarbonamide Nutrition 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- PWAYUHFEKDQEMK-UHFFFAOYSA-N benzene-1,4-diol;phosphoric acid Chemical compound OP(O)(O)=O.OP(O)(O)=O.OC1=CC=C(O)C=C1 PWAYUHFEKDQEMK-UHFFFAOYSA-N 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000020971 citrus fruits Nutrition 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- FKIRSCKRJJUCNI-UHFFFAOYSA-N ethyl 7-bromo-1h-indole-2-carboxylate Chemical compound C1=CC(Br)=C2NC(C(=O)OCC)=CC2=C1 FKIRSCKRJJUCNI-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 235000012438 extruded product Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000012690 ionic polymerization Methods 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- RLAWWYSOJDYHDC-BZSNNMDCSA-N lisinopril Chemical compound C([C@H](N[C@@H](CCCCN)C(=O)N1[C@@H](CCC1)C(O)=O)C(O)=O)CC1=CC=CC=C1 RLAWWYSOJDYHDC-BZSNNMDCSA-N 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- YAFOVCNAQTZDQB-UHFFFAOYSA-N octyl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OCCCCCCCC)OC1=CC=CC=C1 YAFOVCNAQTZDQB-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 235000020636 oyster Nutrition 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000010909 process residue Substances 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000020083 shōchū Nutrition 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000013555 soy sauce Nutrition 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical class NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- KEROTHRUZYBWCY-UHFFFAOYSA-N tridecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C(C)=C KEROTHRUZYBWCY-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 239000001226 triphosphate Substances 0.000 description 1
- 235000011178 triphosphate Nutrition 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- HQUQLFOMPYWACS-UHFFFAOYSA-N tris(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCCl HQUQLFOMPYWACS-UHFFFAOYSA-N 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
Abstract
【課題】熱可塑性樹脂中でのポリテトラフルオロエチレンの分散性を高めることにより成形加工性を改良し、かつ成形時の分解が起こらないポリテトラフルオロエチレン含有粉体及びこれを用いた熱可塑性樹脂組成物を提供すること。
【解決手段】ポリテトラフルオロエチレン（Ａ）と、２−エチルヘキシルアクリレート単量体単位を含有する重合体（Ｂ）とを含有するポリテトラフルオロエチレン含有粉体、及びこの様なポリテトラフルオロエチレン含有粉体と、他の熱可塑性樹脂（Ｃ）とからなる熱可塑性樹脂組成物。
【選択図】 なしA polytetrafluoroethylene-containing powder which is improved in processability by increasing the dispersibility of polytetrafluoroethylene in a thermoplastic resin, and which does not decompose during molding, and a thermoplastic resin using the same. Providing a composition.
A polytetrafluoroethylene-containing powder containing polytetrafluoroethylene (A) and a polymer (B) containing 2-ethylhexyl acrylate monomer units, and a polytetrafluoroethylene-containing powder as described above. A thermoplastic resin composition comprising a powder and another thermoplastic resin (C).
[Selection diagram] None
Description
【０００１】
【発明の属する技術分野】
本発明は、熱可塑性樹脂に添加することにより、その成形加工性、機械的性質などを改良するポリテトラフルオロエチレン含有粉体に関するものである。
【０００２】
【従来の技術】
ポリテトラフルオロエチレン（ＰＴＦＥ）は耐熱性、耐薬品性、電気的絶縁性に優れ、撥水撥油性、非粘着性、自己潤滑性等の特異な表面特性を有するためコーティング剤等に広く用いられている。
また、高結晶性で分子間力が低いためわずかな応力で繊維化する性質を有しており、熱可塑性樹脂に配合すると成形加工性、機械的性質などを改良するため、熱可塑性樹脂用添加剤としても使用されている（例えば特許文献１、２、３）。しかしながらこれらの方法では、いずれもポリテトラフルオロエチレンのマトリックス樹脂中での分散性に問題があり、ポリテトラフルオロエチレンの添加効果を発現させるためには多量のポリテトラフルオロエチレンを添加する必要がある。
【０００３】
このような技術課題に対し、炭素数５〜３０のアルキル（メタ）アクリレートとポリテトラフルオロエチレンとを併用することによってポリテトラフルオロエチレンの分散性を向上させることができる（特許文献４、５、６）。
【特許文献１】特開平５−２１４１８４号公報
【特許文献２】特開平６−３０６２１２号公報
【特許文献３】特開平７−３２４１４７号公報
【特許文献４】特開平１１−６０８７１号公報
【特許文献５】特開平１１−１２４４７８号公報
【特許文献６】特開平１１−１９９７３３号公報
【０００４】
【発明が解決しようとする課題】
しかしながらこれらの公報においては、その実施例において、アルキル（メタ）アクリレートとして、ドデシルおよびトリデシルメタクリレート等を使用しており、熱可塑性樹脂を成型する際ポリテトラフルオロエチレン含有粉体中に含まれる（メタ）アクリレートが分解して分解ガスが発生し、その成形性や物性を低下させたり、異臭が発生するという課題がある。
【０００５】
【課題を解決するための手段】
本発明の目的は、ポリテトラフルオロエチレンの熱可塑性樹脂中での分散性を高めながら、成形加工性を改良し、かつ高温での成形においても分解が起こらず、特異な臭気を発生することがないポリテトラフルオロエチレン含有粉体及びこれを用いた熱可塑性樹脂組成物を提供することにある。
即ち、本発明の要旨はポリテトラフルオロエチレン（Ａ）と、２−エチルヘキシルアクリレート単量体単位を含有する重合体（Ｂ）とを含有するポリテトラフルオロエチレン含有粉体にある。
【０００６】
【発明の実施の形態】
以下、本発明について詳細に説明する。
本発明のポリテトラフルオロエチレン含有粉体は、ポリテトラフルオロエチレン（Ａ）と、２−エチルヘキシルアクリレート単量体単位を含有する重合体（Ｂ）とを含有するものである。
ポリテトラフルオロエチレン含有粉体中のポリテトラフルオロエチレンの含有量は好ましくは１質量％以上、更に好ましくは５質量％以上である。含有量が１質量％未満ではポリテトラフルオロエチレンの添加効果を得るための添加部数が多くなるために経済性が低下する傾向にある。
また、ポリテトラフルオロエチレン含有粉体中のポリテトラフルオロエチレンの含有量は好ましくは７０質量％以下、更に好ましくは５０質量％以下である。含有量が７０質量％を超えるとポリテトラフルオロエチレンの分散性が低下する傾向にある。
【０００７】
本発明のポリテトラフルオロエチレン含有粉体においては、ポリテトラフルオロエチレン（Ａ）が、粒子径で１０μｍを超える凝集体となっていないことが好ましく、粒子径０．０５〜１．０μｍの粒子であることが更に好ましい。
この様な粒子径のポリテトラフルオロエチレン粒子は、含フッ素界面活性剤を用いた乳化重合により、テトラフルオロエチレンを重合させることにより得ることができる。
ポリテトラフルオロエチレン粒子の乳化重合の際、ポリテトラフルオロエチレンの特性を損なわない範囲で、共重合成分としてヘキサフルオロプロピレン、クロロトリフルオロエチレン、フルオロアルキルエチレン、パーフルオロアルキルビニルエーテル等の含フッ素オレフィンや、パーフルオロアルキル（メタ）アクリレート等の含フッ素アルキル（メタ）アクリレートを用いることができる。共重合成分の含量は、テトラフルオロエチレン単量体１００質量部に対して１０質量部以下であることが好ましい。
【０００８】
ポリテトラフルオロエチレン粒子分散液の市販原料としては、旭硝子（株）製フルオンＡＤ−１、ＡＤ−９１１、ＡＤ−９３６、ＡＤ−９３８、ダイキン工業（株）製ポリフロンＤ−１、Ｄ−２、Ｄ−２ＣＥ、Ｄ−２０Ｅ、Ｄ−３Ｅ、Ｄ−３０Ｅ、三井デュポンフロロケミカル（株）製テフロン（登録商標）３０Ｊ等を挙げることができる。
【０００９】
本発明における重合体（Ｂ）は、２−エチルヘキシルアクリレート単量体単位を含有する重合体であり、２−エチルヘキシルアクリレート単量体単位とエチレン性不飽和結合を有する他の単量体単位とからなる共重合体であることが好ましい。
重合体（Ｂ）中における２−エチルヘキシルアクリレート単量体単位の含有量は３０〜８０質量％であることが好ましい。含有量が３０質量％未満では、熱可塑性樹脂中でのポリテトラフルオロエチレンの分散性が低下する傾向にあり、８０質量％を超えるとポリテトラフルオロエチレン含有粉体の粉体取扱い性が悪化する傾向にある。
エチレン性不飽和結合を有する他の単量体としては、ｎ−ブチル（メタ）アクリレート、エチル（メタ）アクリレート、メチル（メタ）アクリレート、（メタ）アクリロニトリル、α−メチルスチレン、スチレン、塩化ビニル、塩化ビニリデンを挙げることができる。
また、重合体（Ｂ）においては、５質量％未満の範囲で、アクリルアミド、アクリル酸、１，３−ブチレングリコールジメタクリレート、１，４−ブチレングリコールジメタクリレート、ジエチレングリコールジメタクリレート、ジピロピレングリコールジメタクリレート、ジビニルベンゼン、エチレングリコールジメタクリレート、イタコン酸、メタクリル酸、Ｎ−メチロールアクリルアマイド、Ｎ−メチロールメタクリルアマイド、４−メチルー１，４−ペンタンジールジメタクリレート、プロピレングリコールジメタクリレート、トリビニルベンゼン、アリルメタクリレート、ｔｅｒｔ−ブチルアクリレート、ｔｅｒｔ−ブチルアミノエチルメタクリレート、ｓｅｃ−ブチルメタクリレート、シクロヘキシルメタクリレート、ジメチルアミノエチルメタクリレート、２−エチルヘキシルメタクリレート、ヒドロヘキシルメタクリレート、ヒドロヘキシルビニルスルフィド、ヒドロキシプロピルメタクリレート、イソボルニルメタクリレート、イソブチルメタクリレート、イソプロピルアクリレート、イソプロピルメタクリレート、メタクリルアミド、ｎ−プロピルメタクリレート、３，５，５−トリメチルシクロヘキシルメタクリレートから選ばれた少なくとも１種の単量体を共重合させたものであってもよい。
【００１０】
本発明に用いる重合体（Ｂ）の製造法は、特に制限されるものではないが、例えば、イオン性乳化剤を用いる乳化重合法、イオン性重合開始剤を用いるソープフリー乳化重合法等を挙げることができる。
イオン性乳化剤としては、アニオン性乳化剤、カチオン性乳化剤、両性イオン乳化剤のいずれを用いてもよい。また所望によりこれらのイオン性乳化剤と共にノニオン性乳化剤を併用してもよい。
中でも、ジオクチルスルホコハク酸ナトリウムは分解時に２−エチルヘキサノールを発生し、ポリ２−エチルヘキシルアクリレートの分解ガスと同じになるために好ましく用いられる。
【００１１】
重合体（Ｂ）の乳化重合分散液中の粒子径ｄは、特に制限されるものではないが、ポリテトラフルオロエチレン粒子との凝集状態の安定性の観点から、ポリテトラフルオロエチレン粒子の粒子径Ｄに対して次式（１）の範囲内にあることが好ましい。
０．１Ｄ＜ｄ＜１０Ｄ ・・・式（１）
【００１２】
本発明のポリテトラフルオロエチレン含有粉体は、前述した粒子径０．０５〜１．０μｍのポリテトラフルオロエチレン（Ａ）粒子分散液と、重合体（Ｂ）粒子分散液とを混合した後、分散液を凝固、乾燥するか、もしくは分散液をスプレードライすることにより粉体として回収することができる。
前述した分散液の凝固は、分散液を酢酸カルシウム、塩化カルシウム、硫酸マグネシウム等の金属塩を溶解した熱水中に投入することにより行うことができ、その後の乾燥は公知の方法により行うことができる。
また、分散液のスプレードライは、分散液を熱風中に噴霧することにより、分散液中の固形分を回収するものであり、公知の方法により行うことができる。
【００１３】
本発明のポリテトラフルオロエチレン含有粉体は、前述したポリテトラフルオロエチレン（Ａ）粒子分散液と重合体（Ｂ）分散液を混合した分散液中に、更にエチレン性不飽和結合を有する単量体を添加、乳化重合して、その後凝固、乾燥するか、若しくは乳化重合後の分散液をスプレードライすることにより粉体として回収したものであってもよい。
このとき用いるエチレン性不飽和結合を有する単量体とは、先に記載した重合体（Ｂ）の共重合成分として用いるエチレン性不飽和結合を有する単量体を同様のものを用いることができる。
また分散液の凝固、乾燥やスプレードライについては、前述した方法と同様に行うことができる。
【００１４】
通常のポリテトラフルオロエチレンファインパウダーは、粒子分散液の状態から粉体として回収する行程で１００μｍ以上の凝集体となってしまうために熱可塑性樹脂に均一に分散させることが困難であるのに対して、前述した２つの方法により得られたポリテトラフルオロエチレン含有粉体は、ポリテトラフルオロエチレンが単独で粒子径１０μｍを超えるドメインを形成していないために熱可塑性樹脂に対する分散性がきわめて優れている。
【００１５】
ポリテトラフルオロエチレン含有粉体を添加できる熱可塑性樹脂（Ｃ）としては、ポリエチレン、ポリプロピレン、エチレンープロピレン共重合体等のポリオレフィン樹脂、ポリエチレンテレフタレート（ＰＥＴ）、ポリエチレンナフタレート、ポリシクロヘキサンテレフタレート、ポリブチレンテレフタレート（ＰＢＴ）、ポリブチレンナフタレート等のポリエステル樹脂、ポリカーボネート（ＰＣ）、ブタジエンゴムグラフト共重合体（例えばＡＢＳ樹脂）、アクリルゴムグラフト共重合体、シリコーン−アクリル複合ゴムグラフト共重合体、エチレンプロピレンゴムグラフト共重合体、ＨＩＰＳ、ＡＳ等のスチレン系樹脂、塩化ビニル樹脂、ポリアセタール樹脂、ポリフェニレンサルファイド樹脂、ポリフェニレンエーテル樹脂（ＰＰＥ）、ナイロン６、ナイロン６６等のポリアミド樹脂（ＰＡ）、ＰＭＭＡ等のアクリル樹脂、ＰＥＴ／ＰＢＴ、ＰＣ／ＰＢＴ、ＰＢＴ／ＡＢＳ、ＰＣ／ＡＢＳ、ＰＡ／ＡＢＳ、ＰＰＥ／ＰＢＴ、ＰＰＥ／ＨＩＰＳ、ＰＰＥ／ＰＡ等が挙げられるが、特にポリオレフィン樹脂に好適に用いられる。
【００１６】
ポリオレフィン樹脂には、ポリプロピレン、ポリエチレン、ポリ−１−ブテン、ポリイソブチレン、プロピレンとエチレンおよび／または１−ブテンとの任意の比率でのランダムまたはブロック共重合体、エチレンとプロピレンとが任意の比率でありジエン成分が５０重量％以下であるエチレン−プロピレン−ジエン３元共重合体、ポリメチルペンテン、エチレンまたはプロピレンと５０重量％以下の酢酸ビニル、（メタ）アクリル酸アルキルエステル、芳香族ビニル化合物などのエチレン性不飽和結合を有するオレフィン以外の単量体とのランダム、ブロックまたはグラフト共重合体などが含まれる。
好ましいポリオレフィンとしては、プロピレンを５０重量％以上含有するプロピレン系ポリオレフィン、プロピレンを５０重量％以上含有するプロピレン系ポリオレフィン１００重量部とエチレンを５０重量％以上含有するエチレン系ポリオレフィン０．１〜１００重量部との混合物が挙げられ、特にＡＳＴＭ Ｄ１２３８によるメルトフローレートが１０ｇ／１０分以下のものが溶融張力が高く加工性が優れるため好ましい。なお、メルトフローレートはＡＳＴＭ Ｄ１２３８に準じてプロピレン系ポリオレフィンでは２３０℃、２．１６ｋｇ荷重で、エチレン系ポリオレフィンでは１９０℃、２．１６ｋｇ荷重で測定される。
【００１７】
本願発明のポリテトラフルオロエチレン含有粉体を熱可塑性樹脂に混合することにより、この熱可塑性樹脂組成物を加工するに際して、溶融時の張力を増大させることができ、カレンダー加工時の引き取り性、熱成型時またはブロー成型時の溶融樹脂のドローダウン、発泡成型時のセルの連泡化などが改良され、カレンダー加工、熱成形、ブロー成形、発泡成形などの加工性が改良される。また、押出成型時の吐出量、シートおよびフィルムなどの押し出し成形体の表面状態が改良され、押し出し加工性が改良されるとともに、ポリテトラフルオロエチレン含有粉体の高温下での分解が低減されているため、高温成形時の成形性にも優れたものとなる。
【００１８】
熱可塑性樹脂（Ｃ）には更に充填剤を添加することもできる。充填剤の配合量は、熱可塑性樹脂（Ｃ）１００質量部に対して、０．１〜４００質量部であることが好ましく、この充填剤の配合により剛性や耐熱性が向上し、カレンダー加工などにおけるロール面への粘着防止などの加工性が改良され、また低コスト化が達成できる。０．１質量部より少ないと剛性改良効果が充分でなく、４００質量部より多いと表面性が低下する傾向がある。充填剤の添加量はより好ましくは１〜３５０質量部、更に好ましくは１〜３００質量部である。
添加する充填剤としては、金属粉、酸化物、水酸化物、珪酸または珪酸塩、炭酸塩、炭化珪素、植物性繊維、動物性繊維、合成繊維などが挙げられ、これらの具体的な代表例としては、アルミニウム粉、銅粉、鉄粉、アルミナ、天然木材、紙、炭酸カルシウム、タルク、硝子繊維、炭酸マグネシウム、マイカ、カオリン、硫酸カルシウム、硫酸バリウム、水酸化アルミニウム、水酸化マグネシウム、シリカ、クレー、ゼオライト、アセテート粉、絹粉、アラミド繊維、アゾジカルボンアミド、グラファイト、および再生充填材材料などが挙げられる。これらは単独で、または２種以上を混合して用いることができる。
上記再生充填材材料としては籾殻、フスマ、米糠、とうもろこし屑、芋ガラ、脱脂大豆、胡桃殻、ココナッツヤシ殻、スソコ、バガス、などの農産廃棄物、焼酎などの蒸留酒の蒸留粕、ビール麦芽粕、ワインブドウ粕、酒粕、醤油粕などの醸造粕、茶滓、コーヒー滓、柑橘絞り滓などの飲料工場からの各種滓、オカラ，クロレラなどの食品加工廃棄物、牡蛎殻などの貝殻、海老や蟹の甲羅などの水産廃棄物、おが屑、廃ほだ木、樹皮、伐採竹、木造家屋の解体などで発生する廃木材などの木質系廃棄物、古紙や製紙業から発生する廃パルプ、紙片などの廃棄物が挙げられる。これらは単独で、または２種以上を混合して用いることができる。
【００１９】
また、熱可塑性樹脂（Ｃ）には、更に必要に応じて安定剤、滑剤、難燃剤、などの添加剤を添加することができる。
用いる安定剤としては、ペンタエリスリチル−テトラキス［３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、トリエチレングリコール−ビス［３−（３−ｔ−ブチル−５−メチル−４−ヒドロキシフェニル）プロピオネート］などのフェノール系安定剤、トリス（モノノニルフェニル）フォスファイト、トリス（２，４−ジ−ｔ−ブチルフェニル）フォスファイトなどのリン系安定剤、ジラウリルチオジプロピオネートなどのイオウ系安定剤、滑剤としては、ラウリル酸、パルミチン酸、オレイン酸またはステアリン酸のナトリウム、カルシウムまたはマグネシウム塩など、また難燃剤としては、トリメチルホスフェート、トリエチルホスフェート、トリブチルホスフェート、トリオクチルホスフェート、トリブトキシエチルホスフェート、トリフェニルホスフェート、トリクレジルホスフェート、クレジルフェニルホスフェート、オクチルジフェニルホスフェート、ジイソプロピルフェニルホスフェート、トリス（クロロエチル）ホスフェート、アルコキシ置換ビスフェノールＡビスホスフェート、ヒドロキノンビスホスフェート、レゾルシンビスホスフェート、トリオキシベンゼントリホスフェート等のポリホスフェートなどのリン酸エステル化合物、テトラブロモビスフェノールＡ、デカブロモジフェニルオキサイド、ヘキサブロモシクロドデカン、オクタブロモジフェニルエーテル、ビストリブロモフェノキシエタン、エチレンビステトラブロモフタイルイミド、トリブロモフェノール、ハロゲン化ビスフェノールＡとエピハロヒドリンとの反応によって得られる各種ハロゲン化エポキシオリゴマー、ハロゲン化ビスフェノールＡを構成成分とするカーボネートオリゴマー、ハロゲン化ポリスチレン、塩素化ポリオレフィンおよびポリ塩化ビニル等のハロゲン含有化合物、金属水酸化物、金属酸化物、スルファミン酸化合物等がそれぞれ代表例として挙げられる。
【００２０】
熱可塑性樹脂にポリテトラフルオロエチレン含有粉体を添加した熱可塑性樹脂組成物を加工する方法としては、カレンダー成形、押出成形、熱成型加工、ブロー成形加工、射出成形加工、発泡成形加工、溶融紡糸などを挙げることができる。
また、熱可塑性樹脂組成物は、シート、フィルム、熱成形体、中空成形体、射出成形体、発泡成形体、繊維などに成型されることができる。
【００２１】
【実施例】
以下、実施例により本発明を具体的に説明するが、本発明はこれら実施例のみに限定されるものではない。なお、各実施例、比較例中の「部」は「質量部」を示す。
なお、本実施例、比較例において各種評価は以下の方法により行った。
（１）難燃性
ペレットを射出成形機（東芝機械（株）製ＩＳ−１００）を用いて試験片に成形し、アンダーライタ−ズラボラトリーズコーポレーションの定めるＵＬ９４−Ｖ規格燃焼試験に準じて測定し、Ｖ−０に合格または不合格として判定した。但し、ＵＬ９４−Ｖ規格燃焼試験片の厚みは１／１６”で行った。
（２）メルトテンション（ＭＴ）
樹脂組成物のペレットを降下式フローテスター（東洋精機製キャピログラフ）を用い、一定押出し量（降下速度１０ｍｍ／分）で押出し，ストランドを一定速度（４ｍ／分）で引き取り、メルトテンションを測定した。ダイスのＬ／Ｄは８．０ｍｍ／Φ２．１ｍｍ、樹脂温度は１９０℃とした。
（３）メルトフローレート（ＭＦＲ）
樹脂組成物のペレットを用いて、ＡＳＴＭ Ｄ１２３８に準じて２３０℃、２．１６ｋｇにて測定した。
（４）分散性
樹脂組成物のペレットを用いて、１００ｍｍ角、３．０ｍｍ厚の角板を射出成形し、ポリテトラフルオロエチレン含有粉体の分散性を目視により判定した。
○：微細で均一
×：不均一
（５）発泡セル状態
発泡樹脂組成物をＳＥＭ観察し、発泡セルの状態を目視により判定した。
○：均一
×：不均一
（６）臭気
押し出し機出口から発生する臭気を嗅ぎ、判定した。
○：良好
△：若干臭い
×：臭い
（７）分解ガス分析
押出し機出口付近のガスを活性炭の入ったチューブで捕集し、クロロホルムにて抽出、ＧＣ／ＭＳ（ヒューレット・パッカード社製６８９０／５９７３）により発生したガスの分析を行った。特定できた分解ガスの内、モノマー及び乳化剤由来のものを記載した。
【００２２】
（製造例１） ポリテトラフルオロエチレン含有粉体（Ｉ）の製造
アクリル酸−２−エチルヘキシル８０部、メタクリル酸メチル２０部の混合溶液にジイソプロピルベンゼンヒドロキシパーオキサイド０．３部を溶解させた。これに乳化剤として、ドデシルベンゼンスルホン酸ナトリウム（「ネオペレックスＧ−１５」、花王（株）製）を固形分換算で２．０部と蒸留水２９５部との混合液を添加し、ホモミキサーにて１０，０００ｒｐｍで５分間攪拌した後、ホモジナイザーに２０ＭＰａの圧力で２回通し、安定な予備分散液を得た。これを攪拌装置、冷却器、熱電対、窒素導入口、試薬滴下装置を備えたフラスコに仕込み、窒素気流下、水浴中６０℃に加熱した。硫酸第一鉄０．０００４部、エチレンジアミン四酢酸二ナトリウム０．００１２部、Ｌ−（＋）−アスコルビン酸０．２部を蒸留水５部に溶かして加えて重合を開始し、３時間保持し、有機系重合体（Ｂ）の分散液を得た。有機系重合体（Ｂ）の分散液の固形分濃度は２５．０％で、粒子径分布は単一のピークを示し、質量平均粒子径は１６０ｎｍであった。また、８３．３部のフルオンＡＤ９３８（旭硝子フルロロポリマーズ（株）製）（固形分濃度６３．０％、ポリテトラフルオロエチレンに対して５％のポリオキシアルキレンアルキルエーテルを含む）に、蒸留水１１６．７部を添加して、固形分２６．２％のポリテトラフルオロエチレン（Ａ）の分散液を得た。ポリテトラフルオロエチレン（Ａ）の分散液は、２５％のポリテトラフルオロエチレンと１．２％のポリオキシアルキレンアルキルエーテルを含むものである。また、ポリテトラフルオロエチレン（Ａ）の分散液中のポリテトラフルオロエチレン（Ａ）の粒子径は、０．３μｍであった。
上記ポリテトラフルオロエチレン（Ａ）の分散液１２０部（ポリテトラフルオロエチレン３０部を含有）と有機系重合体（Ｂ）の分散液２００部（アクリル酸−２−エチルヘキシル／メタクリル酸メチル共重合体５０部）とを攪拌翼、コンデンサー、熱電対、窒素導入口を備えたセパラブルフラスコに仕込み、窒素気流下で１時間攪拌した。その後、系内を８０℃に昇温し、１時間攪拌した後、硫酸鉄（ＩＩ）０．００１部、エチレンジアミン四酢酸二ナトリウム０．００３部、Ｌ−（＋）―アスコルビン酸０．１部、蒸留水６０．８部の混合液を加え、そこにメタクリル酸メチル１９部、アクリル酸メチル１部、ジイソプロピルベンゼンヒドロキシパーオキサイド０．４部の混合液を１時間かけて滴下し、滴下終了後内温を８０℃で１時間保持してラジカル重合を完了させた。
一連の操作を通じて固形物の分離はみられず、均一な混合分散液を得た。この混合分散液を酢酸カルシウム３部を含む９０℃の熱水４００部に投入し、固形物を分離させ、濾過、乾燥してポリテトラフルオロエチレン含有粉体（Ｉ）９９部を得た。
【００２３】
（製造例２）ポリテトラフルオロエチレン含有粉体（ＩＩ）の製造
製造例１の乳化剤をジオクチルスルホコハク酸ナトリウム（花王（株）製「ペレックスＯＴＰ」）を固形分換算で１．０部用いた以外は、製造例１と同様にして、ポリテトラフルオロエチレン含有粉体（ＩＩ）１００部を得た。
なお、有機系重合体（Ｂ）の分散液の固形分濃度は２５．０％で、粒子径分布は単一のピークを示し、質量平均粒子径は２３０ｎｍであった。
【００２４】
（製造例３）ポリテトラフルオロエチレン含有粉体（ＩＩＩ）の製造
２−エチルヘキシルメタクリレートに代えてドデシルメタクリレートを用いたこと以外は製造例１と同様の操作を行い、ポリテトラフルオロエチレン含有粉体（ＩＩＩ）１００部を得た。
【００２５】
（製造例４）ポリテトラフルオロエチレン含有粉体（ＩＶ）の製造
２−エチルヘキシルメタクリレートに代えてドデシルメタクリレートを用いたこと以外は製造例２と同様の操作を行い、ポリテトラフルオロエチレン含有粉体（ＩＶ）１００部を得た。
【００２６】
［実施例１〜２、比較例１〜２］
得られたポリテトラフルオロエチレン含有粉体（Ｉ）〜（ＩＶ）について分解温度を測定した。分解温度の測定にはＳＥＩＫＯ社製ＴＧ／ＤＴＡ２００を用い、窒素フロー：２００ｍｌ／分、温度上昇：１０℃／分で１％重量減少温度、５％重量減少温度を測定した。結果を表１に示す。
本発明のポリテトラフルオロエチレン含有粉体は、分解温度が高く、耐熱性に優れた粉体であることがわかる。
【００２７】
【表１】
［実施例３〜４、比較例３〜４］
ポリカーボネート（三菱エンジニアリングプラスチックス（株）製ユーピロンＳ２０００）とポリテトラフルオロエチレン含有粉体とを表２に示す割合でハンドブレンドした後、二軸押出機（ＷＥＲＮＥＲ＆ＰＦＬＥＩＤＥＲＥＲ社製ＺＳＫ３０）を用いて、バレル温度２６０℃、スクリュー回転数２００ｒｐｍにて溶融混練しペレット状に賦形した。
得られたペレットを用いて各種評価を行った。結果を表２に示す。
【００２９】
【表２】
［実施例５〜６、比較例５〜６］
ポリオレフィンとしてホモポリプロピレンペレット（日本ポリケム（株）製ノバッテックＦＹ−４、メルトフローレート６．０ｇ／１０分）を用い、これとポリテトラフルオロエチレン含有粉体を表１に示す割合でハンドブレンドした後、二軸押出機（ＷＥＲＮＥＲ＆ＰＦＬＥＩＤＥＲＥＲ社製ＺＳＫ３０）を用いて、バレル温度２００℃、スクリュー回転数２００ｒｐｍにて溶融混練してペレット状に賦形した。得られたペレットを用いて各種評価を行った。結果を表３に示す。
【００３１】
【表３】
本発明のポリテトラフルオロエチレン含有粉体においては、熱可塑性樹脂中での分散性が高く、メルトテンション、メルトフローレートを向上させるとともに、成形時における分解が低減されるため、発泡性も向上する。
【００３３】
【発明の効果】
本発明のポリテトラフルオロエチレン含有粉体は、熱可塑性樹脂中への分散性が極めて良好であり、これを配合した熱可塑性樹脂組成物は、溶融時の張力、流動性に優れるとともに、成形時の分解も低減されており、カレンダー加工性、ブロー成形性、発泡成形性などの成型加工性に優れる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a polytetrafluoroethylene-containing powder which is added to a thermoplastic resin to improve its moldability, mechanical properties, and the like.
[0002]
[Prior art]
Polytetrafluoroethylene (PTFE) has excellent heat resistance, chemical resistance, and electrical insulation, and has unique surface properties such as water and oil repellency, non-adhesiveness, and self-lubricating properties. ing.
In addition, it has the property of forming fibers with a small stress due to high crystallinity and low intermolecular force, and when added to a thermoplastic resin, it improves molding workability and mechanical properties. It is also used as an agent (for example, Patent Documents 1, 2, and 3). However, all of these methods have a problem in dispersibility of polytetrafluoroethylene in a matrix resin, and it is necessary to add a large amount of polytetrafluoroethylene in order to exert the effect of adding polytetrafluoroethylene. .
[0003]
With respect to such technical problems, the dispersibility of polytetrafluoroethylene can be improved by using an alkyl (meth) acrylate having 5 to 30 carbon atoms and polytetrafluoroethylene in combination (Patent Documents 4, 5, 6).
[Patent Document 1] JP-A-5-214184 [Patent Document 2] JP-A-6-306212 [Patent Document 3] JP-A-7-324147 [Patent Document 4] JP-A-11-60871 [Patent] Document 5: Japanese Patent Application Laid-Open No. H11-124478 Patent Document 6: Japanese Patent Application Laid-Open No. H11-199733
[Problems to be solved by the invention]
However, in these publications, in the examples, dodecyl and tridecyl methacrylate are used as the alkyl (meth) acrylate, and are contained in the polytetrafluoroethylene-containing powder when the thermoplastic resin is molded ( There is a problem that the (meth) acrylate is decomposed to generate a decomposed gas, thereby deteriorating the moldability and physical properties, and generating an odor.
[0005]
[Means for Solving the Problems]
An object of the present invention is to improve the dispersibility of polytetrafluoroethylene in a thermoplastic resin, improve the moldability, and not decompose even during molding at a high temperature and generate a peculiar odor. It is an object of the present invention to provide a polytetrafluoroethylene-containing powder and a thermoplastic resin composition using the same.
That is, the gist of the present invention is a polytetrafluoroethylene-containing powder containing polytetrafluoroethylene (A) and a polymer (B) containing a 2-ethylhexyl acrylate monomer unit.
[0006]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail.
The polytetrafluoroethylene-containing powder of the present invention contains polytetrafluoroethylene (A) and a polymer (B) containing 2-ethylhexyl acrylate monomer units.
The content of polytetrafluoroethylene in the polytetrafluoroethylene-containing powder is preferably at least 1% by mass, more preferably at least 5% by mass. If the content is less than 1% by mass, the number of parts to be added for obtaining the effect of adding polytetrafluoroethylene tends to increase, so that the economic efficiency tends to decrease.
The content of polytetrafluoroethylene in the polytetrafluoroethylene-containing powder is preferably 70% by mass or less, more preferably 50% by mass or less. If the content exceeds 70% by mass, the dispersibility of polytetrafluoroethylene tends to decrease.
[0007]
In the polytetrafluoroethylene-containing powder of the present invention, the polytetrafluoroethylene (A) preferably does not form an aggregate having a particle diameter of more than 10 μm. More preferably, it is.
Polytetrafluoroethylene particles having such a particle diameter can be obtained by polymerizing tetrafluoroethylene by emulsion polymerization using a fluorinated surfactant.
At the time of emulsion polymerization of polytetrafluoroethylene particles, hexafluoropropylene, chlorotrifluoroethylene, fluoroalkylethylene, and a fluorine-containing olefin such as perfluoroalkylvinyl ether as a copolymerization component, as long as the properties of polytetrafluoroethylene are not impaired. And fluorine-containing alkyl (meth) acrylates such as perfluoroalkyl (meth) acrylate. The content of the copolymer component is preferably 10 parts by mass or less based on 100 parts by mass of the tetrafluoroethylene monomer.
[0008]
Commercially available raw materials for the polytetrafluoroethylene particle dispersion include Fluon AD-1, AD-911, AD-936, and AD-938 manufactured by Asahi Glass Co., Ltd., and Polyflon D-1, D-2 manufactured by Daikin Industries, Ltd. D-2CE, D-20E, D-3E, D-30E and Teflon (registered trademark) 30J manufactured by DuPont-Mitsui Fluorochemicals Co., Ltd. can be exemplified.
[0009]
The polymer (B) in the present invention is a polymer containing a 2-ethylhexyl acrylate monomer unit, and is composed of a 2-ethylhexyl acrylate monomer unit and another monomer unit having an ethylenically unsaturated bond. Is preferable.
The content of the 2-ethylhexyl acrylate monomer unit in the polymer (B) is preferably from 30 to 80% by mass. If the content is less than 30% by mass, the dispersibility of polytetrafluoroethylene in the thermoplastic resin tends to decrease, and if it exceeds 80% by mass, the powder handling property of the polytetrafluoroethylene-containing powder deteriorates. There is a tendency.
Other monomers having an ethylenically unsaturated bond include n-butyl (meth) acrylate, ethyl (meth) acrylate, methyl (meth) acrylate, (meth) acrylonitrile, α-methylstyrene, styrene, vinyl chloride, Vinylidene chloride can be mentioned.
In the range of less than 5% by mass of the polymer (B), acrylamide, acrylic acid, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, diethylene glycol dimethacrylate, dipyrropyrene glycol diacrylate are used. Methacrylate, divinylbenzene, ethylene glycol dimethacrylate, itaconic acid, methacrylic acid, N-methylol acrylamide, N-methylol methacrylamide, 4-methyl-1,4-pentanedyl dimethacrylate, propylene glycol dimethacrylate, trivinylbenzene, allyl Methacrylate, tert-butyl acrylate, tert-butylaminoethyl methacrylate, sec-butyl methacrylate, cyclohexyl methacrylate, dimethyl Minoethyl methacrylate, 2-ethylhexyl methacrylate, hydrohexyl methacrylate, hydrohexyl vinyl sulfide, hydroxypropyl methacrylate, isobornyl methacrylate, isobutyl methacrylate, isopropyl acrylate, isopropyl methacrylate, methacrylamide, n-propyl methacrylate, 3,5,5- It may be obtained by copolymerizing at least one monomer selected from trimethylcyclohexyl methacrylate.
[0010]
The method for producing the polymer (B) used in the present invention is not particularly limited, and examples thereof include an emulsion polymerization method using an ionic emulsifier and a soap-free emulsion polymerization method using an ionic polymerization initiator. Can be.
As the ionic emulsifier, any of an anionic emulsifier, a cationic emulsifier, and an amphoteric ionic emulsifier may be used. If desired, a nonionic emulsifier may be used in combination with these ionic emulsifiers.
Among them, sodium dioctyl sulfosuccinate is preferably used because it generates 2-ethylhexanol at the time of decomposition and becomes the same as the decomposition gas of poly-2-ethylhexyl acrylate.
[0011]
The particle size d of the polymer (B) in the emulsion polymerization dispersion is not particularly limited, but from the viewpoint of the stability of the aggregation state with the polytetrafluoroethylene particles, the particle size d of the polytetrafluoroethylene particles It is preferable that D falls within the range of the following expression (1).
0.1D <d <10D (1)
[0012]
The polytetrafluoroethylene-containing powder of the present invention is obtained by mixing the above-mentioned polytetrafluoroethylene (A) particle dispersion having a particle diameter of 0.05 to 1.0 μm with the polymer (B) particle dispersion, The dispersion can be recovered as a powder by coagulation and drying, or by spray drying the dispersion.
Coagulation of the above-described dispersion can be performed by putting the dispersion into hot water in which metal salts such as calcium acetate, calcium chloride, and magnesium sulfate are dissolved, and subsequent drying can be performed by a known method. it can.
The spray drying of the dispersion is to collect the solid content in the dispersion by spraying the dispersion in hot air, and can be performed by a known method.
[0013]
The polytetrafluoroethylene-containing powder of the present invention is obtained by mixing a polytetrafluoroethylene (A) particle dispersion and a polymer (B) dispersion with a monomer having an ethylenically unsaturated bond. The emulsion may be added and emulsion-polymerized and then coagulated and dried, or may be recovered as a powder by spray-drying the dispersion after emulsion polymerization.
The monomer having an ethylenically unsaturated bond used at this time can be the same as the monomer having an ethylenically unsaturated bond used as a copolymer component of the polymer (B) described above. .
Coagulation, drying and spray drying of the dispersion can be carried out in the same manner as described above.
[0014]
While ordinary polytetrafluoroethylene fine powder becomes an aggregate of 100 μm or more in the process of recovering as a powder from the state of a particle dispersion, it is difficult to uniformly disperse it in a thermoplastic resin. The polytetrafluoroethylene-containing powder obtained by the above-described two methods has extremely excellent dispersibility in a thermoplastic resin because polytetrafluoroethylene alone does not form a domain having a particle diameter of more than 10 μm. I have.
[0015]
Examples of the thermoplastic resin (C) to which the polytetrafluoroethylene-containing powder can be added include polyolefin resins such as polyethylene, polypropylene, and ethylene-propylene copolymer, polyethylene terephthalate (PET), polyethylene naphthalate, polycyclohexane terephthalate, and polybutylene. Polyester resins such as terephthalate (PBT) and polybutylene naphthalate, polycarbonate (PC), butadiene rubber graft copolymer (for example, ABS resin), acrylic rubber graft copolymer, silicone-acryl composite rubber graft copolymer, ethylene propylene Rubber graft copolymers, styrene resins such as HIPS and AS, vinyl chloride resins, polyacetal resins, polyphenylene sulfide resins, polyphenylene ether resins (PP ), Polyamide resin (PA) such as nylon 6, nylon 66, etc., acrylic resin such as PMMA, PET / PBT, PC / PBT, PBT / ABS, PC / ABS, PA / ABS, PPE / PBT, PPE / HIPS, PPE / PA and the like, and are particularly preferably used for polyolefin resins.
[0016]
Polyolefin resins include polypropylene, polyethylene, poly-1-butene, polyisobutylene, random or block copolymers of propylene with ethylene and / or 1-butene at any ratio, and ethylene and propylene at any ratio. Ethylene-propylene-diene terpolymer having a diene component of 50% by weight or less, polymethylpentene, ethylene or propylene and 50% by weight or less of vinyl acetate, alkyl (meth) acrylate, aromatic vinyl compound, etc. And a random, block or graft copolymer with a monomer other than an olefin having an ethylenically unsaturated bond.
Preferred polyolefins include a propylene-based polyolefin containing 50% by weight or more of propylene, 100 parts by weight of a propylene-based polyolefin containing 50% by weight or more of propylene, and 0.1 to 100 parts by weight of an ethylene-based polyolefin containing 50% by weight or more of ethylene. And those having a melt flow rate according to ASTM D1238 of 10 g / 10 min or less are preferred because of high melt tension and excellent workability. The melt flow rate is measured at 230 ° C. and a load of 2.16 kg for propylene-based polyolefin, and at 190 ° C. and a load of 2.16 kg for ethylene-based polyolefin in accordance with ASTM D1238.
[0017]
By mixing the polytetrafluoroethylene-containing powder of the present invention with a thermoplastic resin, when processing the thermoplastic resin composition, the tension during melting can be increased, and the take-up property during calendering can be improved. The drawdown of the molten resin at the time of molding or blow molding, the open cell formation of cells at the time of foam molding, and the like are improved, and the processability such as calendering, thermoforming, blow molding, and foaming is improved. In addition, the discharge rate during extrusion molding, the surface condition of extruded products such as sheets and films have been improved, the extrusion processability has been improved, and decomposition of polytetrafluoroethylene-containing powder at high temperatures has been reduced. Therefore, the moldability during high-temperature molding is also excellent.
[0018]
A filler may be further added to the thermoplastic resin (C). The compounding amount of the filler is preferably 0.1 to 400 parts by mass with respect to 100 parts by mass of the thermoplastic resin (C), and the rigidity and heat resistance are improved by the compounding of the filler, such as calendering. The processability such as prevention of adhesion to the roll surface is improved, and the cost can be reduced. If the amount is less than 0.1 part by mass, the effect of improving the rigidity is not sufficient, and if it is more than 400 parts by mass, the surface properties tend to decrease. The addition amount of the filler is more preferably 1 to 350 parts by mass, and still more preferably 1 to 300 parts by mass.
Examples of the filler to be added include metal powder, oxide, hydroxide, silicic acid or silicate, carbonate, silicon carbide, vegetable fiber, animal fiber, and synthetic fiber, and specific representative examples thereof. As aluminum powder, copper powder, iron powder, alumina, natural wood, paper, calcium carbonate, talc, glass fiber, magnesium carbonate, mica, kaolin, calcium sulfate, barium sulfate, aluminum hydroxide, magnesium hydroxide, silica, Examples include clay, zeolite, acetate powder, silk powder, aramid fiber, azodicarbonamide, graphite, and recycled filler materials. These can be used alone or in combination of two or more.
The above-mentioned recycled filler materials include rice husks, bran, rice bran, corn refuse, sweet potatoes, defatted soybeans, walnut husks, coconut coconut shells, succo, bagasse, etc., agricultural wastes, distilled spirits such as shochu, beer malt Brewing lees such as lees, wine grape lees, sake lees, and soy sauce lees, various kinds of scum from beverage factories such as tea scum, coffee scum, and citrus scum, food processing waste such as okara and chlorella, shells such as oyster hulls, and shrimp Wastes such as fish and crab shells, sawdust, waste wood, bark, felled bamboo, wood-based waste such as waste wood from demolition of wooden houses, etc., waste pulp and paper chips from waste paper and paper industry. Waste. These can be used alone or in combination of two or more.
[0019]
Further, additives such as a stabilizer, a lubricant, and a flame retardant can be further added to the thermoplastic resin (C) as needed.
As the stabilizer used, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3- (3-t-butyl-5- Methyl-4-hydroxyphenyl) propionate], phosphorus stabilizers such as tris (monononylphenyl) phosphite and tris (2,4-di-t-butylphenyl) phosphite, dilaurylthio Sulfur-based stabilizers such as dipropionate, lubricants such as sodium, calcium or magnesium salts of lauric acid, palmitic acid, oleic acid or stearic acid, and flame retardants such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, tributyl phosphate Octyl phosphate, bird Toxiethyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl phenyl phosphate, octyl diphenyl phosphate, diisopropyl phenyl phosphate, tris (chloroethyl) phosphate, alkoxy-substituted bisphenol A bisphosphate, hydroquinone bisphosphate, resorcin bisphosphate, trioxybenzene Phosphate compounds such as polyphosphates such as triphosphate, tetrabromobisphenol A, decabromodiphenyl oxide, hexabromocyclododecane, octabromodiphenyl ether, bistribromophenoxyethane, ethylenebistetrabromophytylimide, tribromophenol, halogen Bisphenol A and Epihalohydrin Various halogenated epoxy oligomers obtained by the reaction, carbonate oligomers containing halogenated bisphenol A as constituents, halogen-containing compounds such as halogenated polystyrene, chlorinated polyolefin and polyvinyl chloride, metal hydroxides, metal oxides, sulfamic acid Compounds and the like are listed as typical examples.
[0020]
Methods for processing a thermoplastic resin composition obtained by adding a polytetrafluoroethylene-containing powder to a thermoplastic resin include calendering, extrusion, thermoforming, blow molding, injection molding, foam molding, and melt spinning. And the like.
Further, the thermoplastic resin composition can be formed into a sheet, a film, a thermoformed article, a hollow molded article, an injection molded article, a foamed molded article, a fiber, or the like.
[0021]
【Example】
Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to only these Examples. In the examples and comparative examples, “parts” indicates “parts by mass”.
In addition, in this Example and a comparative example, various evaluations were performed by the following methods.
(1) Flame-retardant pellets are molded into test pieces using an injection molding machine (IS-100 manufactured by Toshiba Machine Co., Ltd.), and measured according to UL94-V standard combustion test defined by Underwriters Laboratories Corporation. , V-0 as pass or fail. However, the thickness of the UL94-V standard combustion test piece was 1/16 ″.
(2) Melt tension (MT)
The pellets of the resin composition were extruded at a constant extrusion rate (downward speed: 10 mm / min) using a descending flow tester (Capillograph, manufactured by Toyo Seiki Co., Ltd.), the strands were drawn at a constant speed (4 m / min), and the melt tension was measured. The L / D of the die was 8.0 mm / Φ2.1 mm, and the resin temperature was 190 ° C.
(3) Melt flow rate (MFR)
It measured at 230 degreeC and 2.16 kg according to ASTM D1238 using the pellet of the resin composition.
(4) Using a pellet of the dispersible resin composition, a 100 mm square, 3.0 mm thick square plate was injection molded, and the dispersibility of the polytetrafluoroethylene-containing powder was visually determined.
：: Fine and uniform ×: Non-uniform (5) Foam Cell State The foamed resin composition was observed by SEM, and the state of the foam cell was visually determined.
：: uniform ×: non-uniform (6) Odor The odor generated from the outlet of the extruder was smelled and judged.
：: good △: slightly odor x: odor (7) Decomposition gas analysis The gas near the outlet of the extruder was collected by a tube containing activated carbon, extracted with chloroform, and GC / MS (6890/5973 manufactured by Hewlett-Packard Company). ) Was analyzed. Among the cracked gases identified, those derived from monomers and emulsifiers are described.
[0022]
(Production Example 1) Production of polytetrafluoroethylene-containing powder (I) In a mixed solution of 80 parts of 2-ethylhexyl acrylate and 20 parts of methyl methacrylate, 0.3 part of diisopropylbenzene hydroxyperoxide was dissolved. As an emulsifier, a mixed solution of 2.0 parts of sodium dodecylbenzenesulfonate ("Neoperex G-15", manufactured by Kao Corporation) in terms of solid content and 295 parts of distilled water was added to the homomixer. After stirring at 10,000 rpm for 5 minutes, the mixture was passed through a homogenizer twice at a pressure of 20 MPa to obtain a stable preliminary dispersion. This was charged into a flask equipped with a stirrer, a cooler, a thermocouple, a nitrogen inlet, and a reagent dropping device, and heated to 60 ° C. in a water bath under a nitrogen stream. 0.0004 parts of ferrous sulfate, 0.0012 parts of disodium ethylenediaminetetraacetate, and 0.2 parts of L-(+)-ascorbic acid are dissolved in 5 parts of distilled water and added to initiate polymerization, and the mixture is kept for 3 hours. Thus, a dispersion of the organic polymer (B) was obtained. The solid content concentration of the dispersion of the organic polymer (B) was 25.0%, the particle size distribution showed a single peak, and the mass average particle size was 160 nm. In addition, 83.3 parts of Fluon AD938 (manufactured by Asahi Glass Fluoropolymers Co., Ltd.) (concentration of solids: 63.0%, containing polyoxyalkylene alkyl ether of 5% based on polytetrafluoroethylene), and distilled water 116.7 parts were added to obtain a dispersion of polytetrafluoroethylene (A) having a solid content of 26.2%. The dispersion of polytetrafluoroethylene (A) contains 25% of polytetrafluoroethylene and 1.2% of polyoxyalkylene alkyl ether. The particle diameter of polytetrafluoroethylene (A) in the dispersion of polytetrafluoroethylene (A) was 0.3 μm.
120 parts of the dispersion of polytetrafluoroethylene (A) (containing 30 parts of polytetrafluoroethylene) and 200 parts of the dispersion of organic polymer (B) (2-ethylhexyl acrylate / methyl methacrylate copolymer) (50 parts) was charged into a separable flask equipped with a stirring blade, a condenser, a thermocouple, and a nitrogen inlet, and stirred for 1 hour under a nitrogen stream. Thereafter, the temperature of the system was raised to 80 ° C., and the mixture was stirred for 1 hour. Then, 0.001 part of iron (II) sulfate, 0.003 part of disodium ethylenediaminetetraacetate, and 0.1 part of L-(+)-ascorbic acid were used. , A mixed solution of 60.8 parts of distilled water was added, and a mixed solution of 19 parts of methyl methacrylate, 1 part of methyl acrylate, and 0.4 part of diisopropylbenzene hydroxyperoxide was added dropwise over 1 hour. The internal temperature was maintained at 80 ° C. for 1 hour to complete the radical polymerization.
Solid substances were not separated through a series of operations, and a uniform mixed dispersion was obtained. This mixed dispersion was poured into 400 parts of 90 ° C. hot water containing 3 parts of calcium acetate, the solid was separated, filtered and dried to obtain 99 parts of polytetrafluoroethylene-containing powder (I).
[0023]
(Production Example 2) Production of polytetrafluoroethylene-containing powder (II) Except that the emulsifier of Production Example 1 was sodium dioctylsulfosuccinate (“Perex OTP” manufactured by Kao Corporation) in an amount of 1.0 part in terms of solid content. In the same manner as in Production Example 1, 100 parts of polytetrafluoroethylene-containing powder (II) was obtained.
In addition, the solid content concentration of the dispersion liquid of the organic polymer (B) was 25.0%, the particle size distribution showed a single peak, and the mass average particle size was 230 nm.
[0024]
(Production Example 3) Production of polytetrafluoroethylene-containing powder (III) Except that dodecyl methacrylate was used in place of 2-ethylhexyl methacrylate, the same operation as in Production Example 1 was performed to obtain a polytetrafluoroethylene-containing powder ( III) 100 parts are obtained.
[0025]
(Production Example 4) Production of polytetrafluoroethylene-containing powder (IV) Except that dodecyl methacrylate was used instead of 2-ethylhexyl methacrylate, the same operation as in Production Example 2 was carried out to obtain a polytetrafluoroethylene-containing powder (IV). IV) 100 parts were obtained.
[0026]
[Examples 1 and 2, Comparative Examples 1 and 2]
The decomposition temperatures of the obtained polytetrafluoroethylene-containing powders (I) to (IV) were measured. The decomposition temperature was measured using TG / DTA200 manufactured by SEIKO, and the 1% weight loss temperature and the 5% weight loss temperature were measured at a nitrogen flow of 200 ml / min and a temperature rise of 10 ° C./min. Table 1 shows the results.
It can be seen that the polytetrafluoroethylene-containing powder of the present invention has a high decomposition temperature and is excellent in heat resistance.
[0027]
[Table 1]
[Examples 3 and 4, Comparative Examples 3 and 4]
Polycarbonate (Iupilon S2000 manufactured by Mitsubishi Engineering-Plastics Co., Ltd.) and polytetrafluoroethylene-containing powder were hand-blended at the ratio shown in Table 2, and then barrel temperature was measured using a twin-screw extruder (ZSK30 manufactured by WERNER & PFLEIDERER). The mixture was melt-kneaded at 260 ° C. and a screw rotation speed of 200 rpm and formed into pellets.
Various evaluations were performed using the obtained pellets. Table 2 shows the results.
[0029]
[Table 2]
[Examples 5 to 6, Comparative Examples 5 to 6]
Homopolypropylene pellets (Novatec FY-4 manufactured by Nippon Polychem Co., Ltd., melt flow rate 6.0 g / 10 min) were used as the polyolefin, and the resulting mixture was hand-blended with the polytetrafluoroethylene-containing powder at the ratio shown in Table 1. Using a twin-screw extruder (ZSK30 manufactured by WERNER & PFLEIDERER), the mixture was melt-kneaded at a barrel temperature of 200 ° C and a screw rotation speed of 200 rpm, and shaped into pellets. Various evaluations were performed using the obtained pellets. Table 3 shows the results.
[0031]
[Table 3]
In the polytetrafluoroethylene-containing powder of the present invention, the dispersibility in the thermoplastic resin is high, the melt tension is improved, and the melt flow rate is improved. .
[0033]
【The invention's effect】
The polytetrafluoroethylene-containing powder of the present invention has an extremely good dispersibility in a thermoplastic resin, and the thermoplastic resin composition containing the same has excellent tensile strength at the time of melting and excellent fluidity, and also has an excellent dispersibility during molding. Is also reduced, and is excellent in moldability such as calenderability, blow moldability and foam moldability.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003170673A JP2004075987A (en) | 2002-06-17 | 2003-06-16 | Polytetrafluoroethylene-containing powder and thermoplastic resin composition using the same |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002175995 | 2002-06-17 | ||
| JP2003170673A JP2004075987A (en) | 2002-06-17 | 2003-06-16 | Polytetrafluoroethylene-containing powder and thermoplastic resin composition using the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2004075987A true JP2004075987A (en) | 2004-03-11 |
Family
ID=32032425
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003170673A Pending JP2004075987A (en) | 2002-06-17 | 2003-06-16 | Polytetrafluoroethylene-containing powder and thermoplastic resin composition using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2004075987A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005171250A (en) * | 2003-12-04 | 2005-06-30 | Solvay Solexis Spa | TFE copolymer |
| JP2011032454A (en) * | 2009-07-07 | 2011-02-17 | Mitsubishi Rayon Co Ltd | Dispersibility improver, thermoplastic resin composition and formed article |
| JP2016029141A (en) * | 2014-07-17 | 2016-03-03 | ユニチカ株式会社 | Polyamide-based resin composition for injection foaming and injection-foamed molded article |
-
2003
- 2003-06-16 JP JP2003170673A patent/JP2004075987A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005171250A (en) * | 2003-12-04 | 2005-06-30 | Solvay Solexis Spa | TFE copolymer |
| JP2011032454A (en) * | 2009-07-07 | 2011-02-17 | Mitsubishi Rayon Co Ltd | Dispersibility improver, thermoplastic resin composition and formed article |
| JP2016029141A (en) * | 2014-07-17 | 2016-03-03 | ユニチカ株式会社 | Polyamide-based resin composition for injection foaming and injection-foamed molded article |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3909020B2 (en) | Modifier for thermoplastic resin and thermoplastic resin composition using the same | |
| JP3272985B2 (en) | Method for producing mixed powder containing polytetrafluoroethylene | |
| CN1168775C (en) | Melt tension enhancer for polyolefin resin and preparation method thereof | |
| US7029750B2 (en) | Thermoplastic resin composition and production method thereof | |
| CN1161409C (en) | Polytetrafluoroethylene powder mixture, compositions containing it and moldings obtained therefrom | |
| JP2002521547A (en) | Flame retardant polycarbonate / rubber-modified graft copolymer resin blend with metallic appearance | |
| JP3962242B2 (en) | Thermoplastic resin composition and molded body using the same | |
| JP2942888B2 (en) | Melt tension improver for polyolefin resin and method for producing the same | |
| CN1068017C (en) | Polyolefin resin composition | |
| JP2004075987A (en) | Polytetrafluoroethylene-containing powder and thermoplastic resin composition using the same | |
| JP3949922B2 (en) | Method for improving moldability and production method of thermoplastic resin composition | |
| JP2004155946A (en) | Modifier for thermoplastic resin and thermoplastic resin composition and product using the same | |
| CN108026345A (en) | Polyvinyl chloride resin composition and molded article | |
| JP3735316B2 (en) | Method for producing polytetrafluoroethylene-containing mixed powder and thermoplastic resin composition | |
| JPH11209549A (en) | Polytetrafluoroethylene-containing mixed powder, thermoplastic resin composition containing the same, and molded article thereof | |
| JP3260307B2 (en) | How to Recycle Polyolefin Resin Products | |
| JP5673991B2 (en) | Dispersibility improver, thermoplastic resin composition, and molded article | |
| JP2001011314A (en) | Thermoplastic resin composition, production method thereof and molded product thereof | |
| JP3442347B2 (en) | Filler masterbatch and molded article made of thermoplastic resin using the same | |
| JP2005232307A (en) | Polyolefin resin composition modifier, polyolefin resin composition, and molded article | |
| JP5248039B2 (en) | Method for producing polytetrafluoroethylene-containing powder | |
| JP3280904B2 (en) | Polyolefin sheet for thermoforming | |
| JP2005306934A (en) | Thermoplastic resin composition and its masterbatch | |
| JP2003003020A (en) | Thermoplastic resin composition | |
| JP2005112924A (en) | Thermoplastic resin composition |